Novel 4,5-dichloro-imidazole derivatives and their use as plant protection agents

ABSTRACT

A 4,5-dichloro-imidazole derivative of the formula ##STR1## in which X represents a ##STR2## in which R 1  represents hydrogen, alkyl with 1 to 8 carbon atoms, alkenyl with up to 8 carbon atoms or the formyl group, 
     R 3  represents cycloalkyl with 5 to 7 carbon atoms in the ring which is optionally substituted by alkyl with 1 to 6 carbon atoms or represents phenyl which may optionally carry one or more substituents selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylmercapto with 1 to 4 carbon atoms and trifluoromethyl, and 
     R represents alkyl with 1 to 12 carbon atoms or alkenyl or alkynyl each with up to 12 carbon atoms, it being possible for each of these alkyl, alkenyl and alkynyl radicals to carry one or more substituents, or represents cycloalkyl with 5 to 7 carbon atoms in the ring or represents a phenyl radical which is at least disubstituted; 
     and the use of such novel 4,5-dichloro-imidazole derivatives as plant growth protection agents especially as a herbicide, plant growth regulant, insecticide or acaricide.

This is a division, of application Ser. No. 835,095, filed Sept. 21, 1977, now U.S. Pat. No. 4,178,166.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to certain new 4,5-dichloroimidazole derivatives, to a process for their preparation and to their use a plant protection agents, e.g., herbicides, insecticides, acaricides, miticides and plant growth regulants. This invention relates to active compositions of such 4,5-dichloroimidazole derivatives in the form of mixtures of such compounds with solid, liquid and gaseous diluents, especially of the type that forms dispersions, emulsions, or suspensions and to the use of such new 4,5-dichloro-imidazole derivatives as plant protection agents.

2. Discussion of the Prior Art

It has been disclosed in Netherlands patent application Nos. 6,805,899 and 6,805,901 that certain 1-alkoxymethyl-trihalogenoimidazoles possess herbicidal, insecticidal and acaricidal properties. Thus, for example, 1-ethoxymethyl-2,4,5-trichloroimidazole can be employed for combating weeds (as disclosed in Netherlands patent application No. 6,805,899). However, the activity of this compound is not always satisfactory.

SUMMARY OF THE INVENTION

The present invention now provides, as new compound, the 4,5-dichloro-imidazole derivatives of the general formula ##STR3## in which

X represents trifluoromethyl, cyano or a ##STR4## in which

R¹ represents a saturated or unsaturated aliphatic radical, which can be carrying one or more substituents selected from halogen, alkoxy with 1 to 6 carbon atoms and alkylmercapto with 1 to 6 carbon atoms,

R² represents hydrogen, alkyl with 1 to 8 carbon atoms, alkenyl with up to 8 carbon atoms or the formyl group,

R³ represents hydrogen, alkyl with 1 to 8 carbon atoms or alkenyl or alkynyl each with up to 8 carbon atoms, it being possible for each of these alkyl, alkenyl and alkynyl radicals to carry one or more substituents selected selected from alkoxy with 1 to 4 carbon atoms, alkylmercapto with 1 to 4 carbon atoms, phenyl (which may optionally carry one or more substituents selected from halogen, alkyl with 1 to 4 carbon atoms, trifluoromethyl and alkoxy with 1 to 4 carbon atoms), furyl or thienyl, or represents cycloalkyl with 5 to 7 carbon atoms in the ring which is optionally substituted by alkyl with 1 to 6 carbon atoms, or represents phenyl which may optionally carry one or more substituents selected from halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylmercapto with 1 to 4 carbon atoms and trifluoromethyl, or

R² and R³ conjointly with the adjoining nitrogen atom form an optionally substituted 5-membered to 7-membered heterocyclic ring in which 1 to 3 ring members may be selected from oxygen, sulphur and nitrogen, and

R represents alkyl with 1 to 12 carbon atoms or alkenyl or alkynyl each with up to 12 carbon atoms, it being possible for each of these alkyl, alkenyl and alkynyl radicals to carry one or more substituents selected from halogen, alkoxy with 1 to 6 carbon atoms, alkylmercapto with 1 to 6 carbon atoms, cycloalkyl with 5 to 7 carbon atoms in the ring and phenyl (which itself optionally carries one or more substituents selected from alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, halogen and trifluoromethyl), or represents cycloalkyl with 5 to 7 carbon atoms in the ring or represents a phenyl radical which is at least disubstituted.

Surprisingly, the 4,5-dichloro-imidazole derivatives of the formula (I), according to the invention, exhibit a better herbicidal activity than 1-ethoxymethyl-2,4,5-trichloroimidazole, known from the state of the art, which is the nearest active compound of the same type of action. In addition, the compounds according to the invention are very suitable for use as plant growth regulators and for combating insects and acarids, especially mites. The compounds according to the invention thus represent a valuable enrichment of the art.

Preferably, X represents trifluoromethyl, cyano or a group --CO--OR¹ or --CO--NR² R³, in which R¹ represents a saturated or unsaturated aliphatic radical with 1 to 6 carbon atoms (especially straight-chain or branched alkyl with 1 to 6 carbon atoms or straight-chain or branched alkenyl or alkynyl, each with up to 6 carbon atoms), which radical can carry one or more substituents selected from fluorine, chlorine, bromine, alkoxy with 1 to 4 carbon atoms and alkylmercapto with 1 to 4 carbon atoms;

R² represents hydrogen, straight-chain or branched alkyl with 1 to 6 carbon atoms, straight-chain or branched alkenyl with up to 6 carbon atoms or the formyl group;

R³ represents straight chain or branched alkyl with 1 to 6 carbon atoms or straight-chain or branched alkenyl or alkynyl each with up to 6 carbon atoms, it being possible for each of these radicals to carry one or more substituents selected from furyl, thienyl, alkoxy with 1 to 3 carbon atoms, alkylmercapto with 1 to 3 carbon atoms and phenyl which may itself optionally carry one or more substituents selected from fluorine, chlorine, bromine, alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms and trifluoromethyl, or represents a cyclopentyl or cyclohexyl group which is optionally substituted by alkyl with 1 to 4 carbon atoms, or represents phenyl which optionally carries one or more substituents selected from fluorine, chlorine, bromine, alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, alkylmercapto with 1 to 3 carbon atoms and trifluoromethyl; or

R² and R³ conjointly with the adjoining nitrogen atom represent a saturated or unsaturated heterocyclic ring with 5 to 7 ring members, it being possible for the heterocyclic ring also to contain, additionally to the said nitrogen atom already mentioned, 1 or 2 further hetero-atoms selected from oxygen, sulphur and nitrogen atoms (heterocyclic radicals which may be mentioned as examples being pyrrolidinyl, piperidinyl, piperazinyl, hexamethyleneimidinyl, morpholinyl, thiamorpholinyl, 1,2,4-triazinyl and imidazolyl); and

R represents straight-chain or branched alkyl with 1 to 6 carbon atoms or straight-chain or branched alkenyl or alkynyl each with up to 6 carbon atoms, it being possible for each of these radicals to carry one or more substituents selected from fluorine, chlorine, bromine, alkoxy with 1 to 4 carbon atoms, alkylmercapto with 1 to 4 carbon atoms, cycloalkyl with 5 or 6 carbon atoms in the ring and phenyl which itself may optionally carry one or more substituents selected from alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 3 carbon atoms, fluorine, chlorine, bromine and trifluoromethyl, or represents cycloalkyl with 5 or 6 carbon atoms in the ring or phenyl which has identical or different substituents at least in the 2- and 4-positions, the substituents being selected from methyl, halogen (such as fluorine, chlorine or bromine), alkoxy with 1 to 4 carbon atoms and trifluoromethyl.

The present invention also provides a process for the preparation of a 4,5-dichloroimidazole derivative of the formula (I), in which

(A) a 4,5-dichloro-imidazole-2-carboxylic acid derivative of the general formula ##STR5## in which

X has the above-mentioned meaning, is, if desires in the presence of a diluent, reacted with a chloromethyl ether of the general formula

    ClCH.sub.2 --O--R                                          (III),

in which

R has the above-mentioned meaning, the compound (II) being employed as such, in the presence of an acid-binding agent, or in the form of an alkali metal salt, alkaline earth metal salt or amine salt, or

(B) a 1-halogenomethyl-4,5-dichloroimidazole-2-carboxylic acid derivative of the general formula ##STR6## in which

X has the above-mentioned meaning and Hal represents chlorine or bromine, is reacted, if desired, in the presence of a diluent, with an alcohol or phenol of the general formula

    HO--R                                                      (V),

in which

R has the above-mentioned meaning, the compound (V) being employed as such, in the presence of an acid-binding agent, or in the form of an alkali metal salt or alkaline earth metal salt.

If 4,5-dichloro-imidazole-2-carboxylic acid nitrile and chloromethyl methyl ether are used as starting materials in process variant (A), the course of the reaction can be represented by the following equation: ##STR7##

If 1-chloromethyl-2-trifluoromethyl-4,5-dichloroimidazole and isopropanol are used as starting materials in process variant (B), the course of the reaction can be represented by the following equation: ##STR8##

The following may be mentioned individually as examples of the 4,5-dichloro-imidazole-2-carboxylic acid derivatives of the formula (II) which may be used according to the invention: 4,5-dichloro-2-trifluoromethylimidazole, 4,5-dichloro-2-cyano-imidazole, 4,5-dichloro-imidazole-2-carboxylic acid methyl ester, 4,5-dichloro-imidazole-2-carboxylic acid ethyl ester, 4,5-dichloro-imidazole-2-carboxylic acid isopropyl ester, 4,5-dichloro-imidazole-2-carboxylic acid butyl ester, 4,5-dichloro-imidazole-2-carboxylic acid sec.-butyl ester, 4,5-dichloro-imidazole-2-carboxylic acid tert.-butyl ester, 4,5-dichloro-imidazole-2-carboxylic acid neopentyl ester, 4,5-dichloro-imidazole-2-carboxylic acid hexyl ester, 4,5-dichloro-imidazole-2-carboxylic acid 2-chloro-ethyl ester, 4,5-dichloro-imidazole-2-carboxylic acid 2,2,2-trichloroethyl ester, 4,5-dichloro-imidazole-2-carboxylic acid 2-methoxyethyl ester, 4,5-dichloro-imidazole-2-carboxylic acid 2-butoxy-ethyl ester, 4,5-dichloro-imidazole-2-carboxylic acid 2-ethylmercapto-ethyl ester, 4,5-dichloro-imidazole-2-carboxylic acid allyl ester, 4,5-dichloro-imidazole-2-carboxylic acid propargyl ester, 4,5-dichloro-imidazole-2-carboxylic acid 2-methyl-but-3-in-2-yl ester, 4,5-dichloro-imidazole-2-carboxylic acid methylamide, 4,5-dichloro-imidazole-2-carboxylic acid ethylamide, 4,5 -dichloro-imidazole-2-carboxylic acid isopropylamide, 4,5-dichloro-imidazole-2-carboxylic acid sec.-butylamide, 4,5-dichloro-imidazole-2-carboxylic acid tert.-butylamide, 4,5-dichloro-imidazole-2-carboxylic acid allylamide, 4,5-dichloro-imidazole-2-carboxylic acid 2-methyl-but-3-in-2-yl amide, 4,5-dichloro-imidazole-2-carboxylic acid 2-ethoxy-ethylamide, 4,5-dichloro-imidazole-2-carboxylic acid 3-methoxy-propylamide, 4,5-dichloro-imidazole-2-carboxylic acid 2-methylmercapto-ethylamide, 4,5-dichloro-imidazole-2-carboxylic acid benzylamide, 4,5-dichloro-imidazole-2-carboxylic acid 4-chlorobenzylamide, 4,5-dichloro-imidazole-2-carboxylic acid 4-methylbenzylamide, 4,5-dichloro-imidazole-2-carboxylic acid 4-trifluoromethyl-benzylamide, 4,5-dichloro-imidazole-2-carboxylic acid 4-methoxy-benzylamide, 4,5-dichloro-imidazole-2-carboxylic acid cyclopentylamide, 4,5-dichloro-imidazole-2-carboxylic acid cyclohexylamide, 4,5-dichloro-imidazole-2-carboxylic acid anilide, 4,5-dichloro-imidazole-2-carboxylic acid 4-chloroanilide, 4,5-dichloro-imidazole-2-carboxylic acid 3,4-dichloro-anilide, 4,5-dichloro-imidazole-2-carboxylic acid 4-methyl-anilide, 4,5-dichloro-imidazole-2-carboxylic acid 4-methoxy-anilide, 4,5-dichloro-imidaziole-2-carboxylic acid 4-chloro-3-trifluoromethyl-anilide, 4,5-dichloro-imidazole-2-carboxylic acid 2-furyl-methylamide, 4,5-dichloro-imidazole-2-carboxylic acid 2-thienylmethylamide, 4,5-dichloro-imidazole-2-carboxylic acid dimethylamide, 4,5-dichloro-imidazole-2-carboxylic acid diethylamide, 4,5-dichloro-imidazole-2-carboxylic acid diisopropylamide, 4,5-dichloro-imidazole-2-carboxylic acid N-methylbutylamide, 4,5-dichloro-imidazole-2-carboxylic acid N-methylcyclohexylamide, 4,5-dichloro-imidazole-2-carboxylic acid N-methyl-anilide, 4,5-dichloro-imidazole-2-carboxylic acid N-formyl-methylamide, 4,5-dichloro-imidazole-2-carboxylic acid N-formyl-isopropylamide, 4,5-dichloro-imidazole-2-carboxylic acid pyrrolidide, 4,5-dichloride-imidazole-2-carboxylic acid piperidide, 4,5-dichloro-imidazole-2-carboxylic acid hexamethyleneimide, 4,5-dichloro-imidazole-2-carboxylic acid morpholide and 4,5-dichloro-imidazole-2-carboxylic acid thiamorpholide.

The 4,5-dichloro-imidazole-2-carboxylic acid derivatives of the formula (II) required as starting compounds have not previously been described in the literature. However, they can be prepared in a simple manner starting from 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) 4,5-dichloro-2-trichloromethyl-imidazole of the formula (VII) or the compound of the formula (VIII). ##STR9## Thus, for example, 4,5-dichloro-2-trifluoromethyl-imidazole is obtained by reacting 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) or 4,5-dichloro-2-trichloromethyl-imidazole of the formula (VII) with excess hydrogen fluoride, if appropriate in the presence of an inert diluent, at temperatures between 0° C. and 200° C., preferably between 20° C. and 150° C. The reaction product is isolated by stripping off the excess hydrogen fluoride after completion of the reaction, dissolving the residue in tetrahydrofuran, adding sodium fluoride and then filtering and distilling the mixture.

Expressed in terms of formulas, the course of this reaction can be illustrated as follows: ##STR10##

4,5-Dichloro-2-cyano-imidazole can be prepared by reacting 4,5-dichloro-2-trichloromethyl-imidazole of the formula (VII) with excess ammonia, if desired, in the presence of a diluent, such as, for example, dioxan, tetrahydrofuran or ethanol, at temperatures between -20° C. and +50° C. Working up is effected by filtering off the insoluble constituents after completion of the reaction, evaporating the filtrate, dissolving the combined residues in hot water and precipitating the product by acidifying with dilute mineral acid.

Expressed in terms of formulas, the course of this reaction can be illustrated as follows: ##STR11##

Those compounds of the formula (II) in which X represents the ##STR12## can be prepared by reacting 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) or 4,5-dichloro-2-trichloromethyl-imidazole of the formula (VII) with alcohols of the formula

    R.sup.1 --OH                                               (IX)

in which

R¹ has the meaning stated above,

if desired, in the presence of an acid-binding agent, for example an alkali metal hydroxide or carbonate or alkaline earth metal hydroxide or carbonate or a tertiary amine, and, if desired, in the presence of an inert diluent, for example, benzine (gasoline), carbon tetrachloride, toluene, chlorobenzene, diethyl ether, tetrahydrofuran or dioxane, at temperatures between 0° C. and 150° C. The reaction products are in general isolated by distilling off the volatile constituents after completion of the reaction, and, if appropriate, purifying the product which thus remains, by recrystallisation.

Expressed in terms of formulas, the course of this reaction can be illustrated as follows: ##STR13##

Those compounds of the formula (II) in which X represents a ##STR14## can be prepared by reacting 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) with, per mole, at least 2 moles of a formic acid amide of the formula ##STR15## in which

R³ has the meaning stated above,

if desired in the presence of a diluent, such as, for example, an aliphatic or aromatic hydrocarbon, an open-chain or cyclic ether or an aliphatic nitrile, at temperatures between -10° C. and +110° C. The working up is effected by pouring the reaction mixture, after completion of the reaction, into ice water. Hereupon, the product precipitates in a crystalline form.

Expressed in terms of formulas, the course of this reaction can be illustrated as follows: ##STR16##

If, in the reaction described above, at least 1 mole of water is furthermore added per mole of 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI), a compound of the formula (II), in which R² represents hydrogen, is obtained directly, at a reaction temperature of between 50° C. and 150° C., in a one-vessel process.

Expressed in terms of formulas, the course of this reaction can be illustrated as follows: ##STR17##

Those compounds of the formula (II) in which X represents a ##STR18## can be prepared by (a) reacting 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) or 4,5-dichloro-2-trichloromethylimidazole of the formula (VII), in a first stage, with an amine hydrochloride of the formula ##STR19## in which

R² and R³ have the meanings stated above,

in the presence of an aprotic solvent, such as a cyclic ether, for example, tetrahydrofuran or dioxane, at temperatures between 50° C. and 200° C., and then, in a second stage, treating the resulting intermediate product, without prior isolation, with water at temperatures between 0° C. and 100° C., or by

(b) reacting the compound of the formula (VIII) with an amine of the formula ##STR20## in which

R² and R³ have the meanings stated above,

if desired in the presence of a diluent, such as, for example, water, alcohol, ether, ketone, aliphatic or aromatic hydrocarbons, dimethylformamide or dimethylsulphoxide, at temperatures between -20° C. and +120° C.

Both in the process according to variant (a) and in the process according to variant (b), working up takes place by pouring the reaction mixture, after completion of the reaction, into water, if necessary whilst cooling. Hereupon, the product is obtained in a solid form.

Expressed in terms of formulas, the course of the reactions according to process variants (a) and (b) can be illustrated as follows: ##STR21##

The 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) is already known (see German Offenlegungsschrift (German Published Specification) No. 2,454,326).

The 4,5-dichloro-2-trichloromethyl-imidaozle of the formula (VII) has not previously been described in the literature. However, it can be prepared in a simple manner by treating 4,5-dichloro-2-dichloromethylene-imidazole of the formula with dry hydrogen chloride at temperatures between -20° C. and +100° C., if desired in the presence of a diluent. Suitable diluents for this are all inert organic solvents, especially aliphatic or aromatic hydrocarbons or halogeno-hydrocarbons, such as, for example, benzine (gasoline), benzene, toluene, methylene chloride, chloroform, carbon tetrachloride or chlorobenzene, and ethers such as, for example, diethyl ether, dibutyl ether, tetrahydrofuran and dioxan

The compound of the formula ##STR22## has not previously been described in the literature. However, it can be prepared in a simple manner by treating 4,5-dichloro-2-dichloromethylene-imidazole of the formula (VI) with water at temperatures between 0° C. and 100° C.

The compounds of the formulas (IX), (XI), (XIV) and (XV) also required as starting materials in preparing the compounds of the formula (II) are known or can be prepared in accordance with processes which have already been described.

The chloromethyl ethers of the formula (III) are already known. The following may be mentioned as individual examples: chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl propyl ether, chloromethyl isopropyl ether, chloromethyl butyl ether, chloromethyl isobutyl ether, chloromethyl hexyl ether, chloromethyl 2-methoxy-ethyl ether, chloromethyl 2-chloroethyl ether, chloromethyl 2,2,2-trichloroethyl ether, chloromethyl 2-ethylmercapto-ethyl ether, chloromethyl allyl ether, chloromethyl cyclohexylmethyl ether, chloromethyl benzyl ether, chloromethyl 4-chlorobenzyl ether, chloromethyl 4-methoxy-benzyl ether, chloromethyl 4-methyl-benzyl ether, chloromethyl-3-trifluoromethyl-benzyl ether, chloromethyl cyclopentyl ether, chloromethyl cyclohexyl ether, chloromethyl 2,4-dichloro-phenyl ether, chloromethyl 2,4,6-trichloro-phenyl ether and chloromethyl 2-methyl-4-chloro-phenyl ether.

The 1-halogenomethyl-4,5-dichloro-imidazole-2-carboxylic acid derivatives of the formula (IV) have not previously been described in the literature. However, they can be prepared in a simple manner by, in a first stage, reacting 4,5-dichloro-imidazole-2-carboxylic acid derivatives of the formula ##STR23## in which

X was the above-mentioned meaning,

with aqueous formaldehyde solution, if desired in the presence of a diluent and, if desired, in the presence of a catalytic amount of a mineral acid, such as, for example, hydrochloric acid or sulphuric acid, at temperatures between 20° C. and 100° C., and then, in a second stage, reacting the compounds thus obtained, of the formula ##STR24## in which

X has the above-mentioned meaning,

with an acid halide, for example a phosphorus(III) halide, such as phosphorus trichloride or phosphorus tribromide, or a thionyl halide, such as thionyl chloride or thionyl bromide, if desired in the presence of an inert diluent, for example a hydrocarbon, halogenohydrocarbon or ether, at temperatures between 0° C. and 100° C., preferably between 10° C. and 75° C. The compounds of the formulae (XVII) and (IV) are isolated in accordance with customary methods.

In terms of formulae, the course of this reaction can be illustrated as follows: ##STR25## in which

Hal is chloride or bromine.

The alcohols and phenols of the formula (V) are already known.

In carrying out the process of the invention in accordance with variant (A), possible diluents are all inert organic solvents, especially aliphatic and aromatic hydrocarbons and halogenohydrocarbons, such as benzine, benzene, toluene, methylene, chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, such as diethyl ether, tetrahydrofuran and dioxan; ketones, such as acetone and methyl isopropyl ketone; alcohols such as methanol, ethanol or tert.-butanol; carboxylic acid esters such as ethyl acetate; and strongly polar solvents such as dimethylformamide and acetonitrile. At times, water, or a mixture of water and an organic solvent, can also be employed.

All customary acid acceptors can be used as acid-binding agents in variant (A) of the process according to the invention. These preferentially include alkali metal hydroxides, alkaline earth metal oxides and alkaline earth metal hydroxides, alkali metal carbonates and alkaline earth metal carbonates and also tertiary amines, such as triethylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine and pyridine.

In the reaction according to process variant (A), the reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at temperatures of from -20° C. to +120° C., preferably from 0° C. to +75° C.

In carrying out the process of the invention in accordance with variant (A), 1 mole, or a slight excess, of a chloromethyl ether of the formula (III) and at least 1 equivalent of acid-binding agent are employed per mole of a 4,5-dichloro-imidazole-2-carboxylic acid derivative of the formula (II). However, it is also possible first to convert the 4,5-dichloro-imidazole-2-carboxylic acid derivative of the formula (II) into an alkali metal salt, alkaline earth metal salt or amine salt in accordance with customary methods and then to react the salt with an equimolar amount of a chloromethyl ether of the formula (III). In these cases, the addition of an acid-binding agent is superfluous.

The isolation of the reaction product may be carried out in accordance with customary methods. In general, the procedure followed is that after completion of the reaction the salts formed are filtered off, the filtrate is evaporated and the residue is either distilled or is purified by treatment with water and, if desired, is additionally also recrystallised. However, it is also possible to dilute the reaction mixture with water after completion of the reaction and to filter off the compounds of the formula (I) which are hereupon obtained in a crystalline form, and recrystallise them if appropriate.

In carrying out the process of the invention in accordance with variant (B), suitable diluents are all inert organic solvents, especially aliphatic and aromatic hydrocarbons and halogenohydrocarbons, such as benzine, benzene, toluene, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, such as diethyl ether, tetrahydrofuran and dioxan; and ketones, such as acetone and methyl isopropyl ketone. Furthermore, an excess of the reactant of the formula (V) can also function as the diluent.

All customary acid acceptors can be used as acid-binding agents in variant (B) of the process according to the invention, especially those acid-binding agents which have already been mentioned preferentially in connection with variant (A) of the process according to the invention.

In the reaction according to variant (B) of the process of the invention, the reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at temperatures of from -20° C. to +120° C., preferably from 0° C. to 100° C.

In carrying out the process of the invention in accordance with variant (B), 1 mole or an excess of an alcohol or phenol of the formula (V) and at least 1 equivalent of acid-binding agent are employed per mole of a 1-halogenomethyl-4,5-dichloro-imidazole-2-carboxylic acid derivative of the formula (IV). It is however also possible first to convert the compound of the formula (V) in accordance with customary methods into an alkali metal derivative or alkaline earth metal derivatives and then to react the said derivative--if appropriate after first isolating it--with an equimolar amount of 1-halogenomethyl-4,5-dichloroimidazole-2-carboxylic acid derivative of the formula (IV). In these cases, the addition of an acid-binding agent is superfluous. The reaction products may be isolated in accordance with customary methods. In general, the procedure followed is as described above in connection with variant (A) of the process according to the invention.

The following may be mentioned individually as examples of the compounds according to the invention: 1-methoxymethyl-2-trifluoromethyl-4,5-dichloro-imidazole, 1-methoxymethyl-2-cyano-4,5-dichloro-imidazole, 1-ethoxymethyl-2-cyano-4,5-dichloro-imidazole, 1-propoxymethyl-2-cyano-4,5-dichloro-imidazole, 1-isopropoxymethyl-2-cyano-4,5-dichloro-imidazole, 1-isobutoxymethyl-2-cyano-4,5-dichloro-imidazole, 1-hexyloxymethyl-2-cyano-4,5-dichloro-imidazole, 1-(2-methoxyethoxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-(2-chloroethoxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-(2,2,2-trichloro-ethoxy)-methyl-2-cyano-4,5-dichloroimidazole, 1-(2-ethylmercapto-ethoxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-allyloxymethyl-2-cyano-4,5-dichloro-imidazole, 1-cyclohexylmethoxy-methyl-2-cyano-4,5-dichloro-imidazole, 1-benzyloxy-methyl-2-cyano-4,5-dichloro-imidazole, 1-(4-chloro-benzyloxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-(4-methoxy-benzyloxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-(4-methyl-benzyloxy)-methyl-2-cyano-4,5-dichloro-imidazole,

1-(3-trifluoromethyl-benzyloxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-cyclopentyloxymethyl-2-cyano-4,5-dichloro-imidazole, 1-cyclohexyloxymethyl-2-cyano-4,5-dichloro-imidazole, 1-(2,4-dichlorophenoxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-(2,4,6-trichlorophenoxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-(2-methyl-4-chloro-phenoxy)-methyl-2-cyano-4,5-dichloro-imidazole, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid methyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid ethyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid isopropyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid butyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid sec.-butyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid tert.-butyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid neopentyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid hexyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-chloroethyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2,2,2-trichloroethyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-methoxy-ethyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-butoxy-ethyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-ethylmercapto-ethyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2 -carboxylic acid allyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid propargyl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-methyl-but-3-in-2-yl ester, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid methylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid ethylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid isopropylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid sec.-butylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid tert.butylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid allylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-methyl-but-3-inyl-2-amide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-ethoxy-ethylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 3-methoxypropylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 2-methylmercapto-ethylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid benzylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-chlorobenzylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-methyl-benzylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-trifluoromethylbenzylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-methoxy-benzylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid cyclopentylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid cyclohexylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid anilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-chloroanilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 3,4-dichloroanilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-methyl-anilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-methoxy-anilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid 4-chloro-3-trifluoromethyl-anilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid furyl-2-methylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid thienyl-2-methylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid dimethylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid diethylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid diisopropylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid N-methyl-butylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid N-methyl-cyclohexylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid N-methyl-anilide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid N-formyl-methylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid N-formyl-isopropylamide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid pyrrolidide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid piperidide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid hexamethyleneimide, 1-ethoxymethyl-4,5-dichloro-imidazole-2-carboxylic acid morpholide and thiamorpholide.

The compounds according to the invention, of the formula (I), can be used as plant protection agents. They are, above all, suitable for use as herbicides. In addition, they can also be employed as plant growth regulators and for combating insects and acarids, especially mites.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, agents for destroying broad-leaved plants and grasses, germination inhibitors and, above all, weedkillers. Whether the compounds according to the invention act as total herbicides or selective hericides depends essentially on the amount used.

By "weeds" in the broadest sense there are meant plants growing in locations where they are not desired.

The active compounds according to the present invention may be used, for example, to combat the following plants:

dicotyledon weeds such as mustard (Sinapis), cress (Lepidium), bed straw (Galium), chickweed (Stellaria), camomile (Matricaria), mayweed (Anthemia), gallant soldier (Galinsoga), goosefoot (Chenopodium), annual nettle (Urtica), groundsel (Senecio), pigweed (Amaranthus), purslane (Portulaca), cocklebur (Xanthium), bindweed (Convolulus), morning glory (Ipomoea), knotweed (Polygonum), sesbania (Sesbania), ragweed (Ambrosia), spear thistle (Cirsium), common thistle (Carduus), sow thistle (Sonchus), field cress (Rorippa), toothcup (Rotala), false pimpernel (Linderna), deadnettle (Lamium), speedwell (Veronica), mallow (Abutilon), emex (Emex), thornapple (Datura), violet (Viola), hemp-nettle (Galeopsis), poppy (Papaver) and knapweed (Centaurea); and

monocotyledon weeds such as barnyard grass (Echinochloa), foxtail (Setaria), wild millet (Panicum), crabgrass (Digitaria), timothy (Phleum), bluegrass (Poa), fescue (Festuca), goosegrass (Eleusine), signalgrass (Brachiaria), ryegrass (Lolium), cheat (Bromus), oats (Avena), flatsedge (Cyperus), sorghun (Sorghum), quackgrass (Agropyron), Bermuda grass (Cynodon), Monocharia, fimbristylis (Fimbristylis), arrowhead (Sagittaria), spikerush (Eleocharis), bulrush (Scirpus), paspalum (Paspalm), Ischaemum, gooseweed (Sphenoclea), crowfoot grass (Dactyloctenium), redtop (Agrostis), meadow foxtail (Alopecurus) and silky bent-grass (Apera).

The active compounds according to the present invention may be used, for example, as selective herbicides in the following cultures:

dicotyledon cultures such as cotton (Gossypium), soy bean (Glycine), beet (Beta), carrot (Daucus), bean (Phaseolus), pea (Pisum), potato (Solanum), flx (Linum), sweet potato (Ipomoea), broad bean (Vicia), tobacco (Nicotiana), tomato (Lycopersicon), groundnut (Arachis), cabbage (Brassica), lettuce (Lactuca), cucumber (Cucumis) and marrow (Cucurbita); and

monocotyledon cultures such as rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugar cane (Saccharum), pineapple (Ananas), asparagus (Asparagus) and onion (Allium).

However, the use of the active compound according to the invention is in no way restricted to these plants or even to the indicated genera but also embraces other plants, in the same way.

Depending on the concentration, the compounds can be used for the total combating of weeds, for example on industrial terrain and railway tracks and on paths and squares with and without trees. Equally, the compounds can be employed for combating weeds in perennial cultures, for example forestry plantings, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulation or compositions with conventional inert (i.e. plant compatible) herbicide or plant growth regulant diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, wettable powders, suspensions, powder dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions, for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.

These are prepared in known manner, for instance by extending the active compounds with conventional herbicides or plant growth regulants dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional H or PGR surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as halogenated hydrocarbons (dichlorodifluoromethane or trichlorofluoromethane) as well as butane, propane, nitrogen and carbon dioxide; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.), as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as solid carriers, ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; as solid carriers for granules; crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and graunles of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; whereas the following may be chiefly considered for use as conventional carrier assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydroylzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially other plant protection agents, such as other insecticides, acaricides, fungicides, bactericides, rodenticides and fertilizers, if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferably 0.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between 0.0000001-100, preferably 0.01-10%, by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a conventional dispersible carrier such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95%, by weight of the mixture.

The amount of active compound used can vary within a fairly wide range. It depends essentially on the nature of the desired effect. In general, the amounts used are from 0.1 to 20 kg of active compound per hectare, preferably from 0.2 to 15 kg/ha, in particular fom 2 to 10 kg/ha.

The compounds according to the invention are especially suitable for the selective combating of weeds in crops of cultured plants such as cereals, cotton and maize.

They may be used both in accordance with the preemergence process and in accordance with the post-emergence process.

The present invention also provides a herbicidal, plant-growth-regulating, insecticidal or acaricidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquified gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The present invention also provides a method of combating weeds, insects or acrids which comprises applying to the weeds, insects or acaride, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention also provides a method of regulating the growth of plants which comprises applying to the plants, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage by weeds, insects or acarids by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.

The present invention further provides plants, the growth of which has been regulated by their being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.

It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.

The herbicidal activity of the compounds of this invention is illustrated by the following biotest Examples.

In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.

The known comparison compounds are identified as follows: ##STR26##

EXAMPLE A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

Seeds of the test plants were sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It was expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation was of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants was determined in % damage in comparison to the development of the untreated control. The figures denoted:

0%=no action (like untreated control)

100%=total destruction

The active compounds, the amounts applied and the results can be seen from the table which follows:

                                      TABLE A                                      __________________________________________________________________________              Amount of                                                                      active com-                                                                    pound used,                                                                          Sina-                                                                              Echino-                                                                             Cheno-                                                                             Stella- Galin-                                                                             Matri-                                 Active compound                                                                         kg/ha pis chloa                                                                               podium                                                                             ria Lolium                                                                             soga                                                                               caria                                                                              Cotton                                                                             Wheat                                                                              Maize                      __________________________________________________________________________     (A)      5     100 40   100 100 80  100 100 80  80  60                         (1)      5     100 80   100 100 100 100 100 60  80  60                         (4)      5     80  80   100 100 80  100 80  0   60  0                          (3)      5     100 100  100 100 80  100 80  40  60  60                         (11)     5     80  80   100 100 80   90 100 0   0   40                         (19)     5     100 80   100 100 80  100 100 80  60  60                         (20)     5     100 80   100 100 100 100 100 80  60  0                          (26)     5     100 100  100 100 100 100 100 80  80  40                         (25)     5     100 100  100 100 100 100 100 80  60  60                         (2)      5     100 100  100 100 100 --  60  80  80  60                         (9)      5     100 100  100 100 100 --  100 100 80  70                         __________________________________________________________________________

EXAMPLE B

Post-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was then diluted with water to the desired concentration.

Test plants which had a height of 5-15 cm were sprayed with the preparation of the active compound in such a way as to apply the amounts of active compound per unit area which are indicated in the table. The concentration of the spray liquor was so chosen that the amounts of active compound shown in the table were applied in 2,000 l of water/ha. After three weeks, the degree of damage to the plants was rated in % damage in comparison to the development of the untreated control. The figures denoted:

0%=no action (like untreated control)

100%=total destruction.

The active compounds, the amounts applied and the results can be seen from the table which follows:

                                      TABLE B                                      __________________________________________________________________________              Amount of                                                                      active com-                                                                    pound used,                                                                          Cheno-                                                                             Sina-                                                                              Galin-                                                                             Stella-                                             Active compound                                                                         kg/ha podium                                                                             pis soga                                                                               ria Urtica                                                                             Daucus                                                                             Oats                                                                               Cotton                                                                             Wheat                           __________________________________________________________________________     (A)      2     100 100 0   0   100 20  60  20  60                              (1)      2     100 100 40  100 100 100 60  0   0                               (4)      2     100 40  40  90   80 40  60  0   60                              (3)      2     60  100 0   40  --  40  0   40  80                              (11)     2     100 100 100 100 --  0   0   0   80                              (20)     2     100 100 100 100 --  60  60  40  60                              (26)     2     100 100 100 100 --  90  90  60  80                              (25)     2     100 100 90  60  --  40  0   80  60                              (9)      2     100 100 90  100 --  60  40  100 80                              __________________________________________________________________________

EXAMPLE C

Insecticidal and Acaricidal Activity

Even when applied at low dosages, Compound (2) is very effective for combating flies (Musca domestica) and aphids (Doralis fabae).

Compounds (35), (36) and (37) show a very good activity against Plutella maculipennis.

Compounds (16), (19), (20) and (26) show a very good activity against Plutella maculipennis, Phaedon cochleariae and Tetranychus urtical.

Compound (1) shows a very good activity against Musca domestica, Doralis fabae, Plutella maculipennis, Tetranychus urtical, Sitophilus granarius and Blattella germanica.

The process of the present invention is illustrated by the following preparative Examples.

EXAMPLE 1 ##STR27##

(i) 16.2 g (0.1 mol) of 2-cyano-4,5-dichloro-imidazole were dissolved in 100 ml of dioxan. 9 g of concentrated (44% strength) aqueous sodium hydroxide solution were added thereto and 10.4 g (0.11 mol) of chloromethyl ethyl ether were then added dropwise at room temperature, whilst stirring. The mixture was stirred further, first for 1 hour at room temperature and then for 1 hour at 40° C., and was thereafter diluted with 250 ml of water. The crystals which had separated out were filtered off and dried. 17.5 g (79.5.% of theory) of 1-ethoxymethyl-2-cyano-4,5-dichloroimidazole, having a melting point of 38°-40° C. after recrystallisation from ligroin, were obtained. Alternative methods for the preparation of compound (1):

(ii) 16.2 g (0.1 mol) of 2-cyano-4,5-dichloro-imidazole were dissolved in 100 ml of acetonitrile. 10.4 g (0.11 mol) of chloromethyl ethyl ether were added at room temperature and 13.8 g (0.1 mol) of dry potassium carbonate were then introduced in portions. The mixture was gradually warmed to the boil and was then boiled under reflux until the evolution of carbon dioxide had ended. The insoluble constituents were filtered off, the filtrate was evaporated in vacuo, water was added to the residue and the mixture was cooled in ice. The crystals obtained were filtered off and dried. 18.3 g (83% of theory) of 1-ethoxymethyl-2-cyano-4,5-dichloro-imidazole, having a melting point of 38°-40° C. after recrystallisation from ligroin, were obtained.

(iii) 18.4 g (0.1 mol) of the sodium salt of 2-cyano-4,5-dichloro-imidazole (prepared from 16.2 g of 2-cyano-4,5-dichloro-imidazole and 2.3 g of sodium in methanol, followed by evaporation to dryness) were suspended in 100 ml of toluene. 10.4 g (0.11 mol) of chloromethyl ethyl ether were added dropwise at room temperature, whilst stirring. The mixture was gradually warmed to the boil and was boiled for a further 2 hours under reflux. The salt-like constituents were filtered off and the filtrate was evaporated in vacuo. 20.5 g (93% of theory) of 1-ethoxymethyl-2-cyano-4,5-dichloro-imidazole remain as the residue, which had a melting point of 38°-40° C. after recrystallisation from ligroin.

The compounds listed in Table 1 below were obtained in accordance with methods analogous to those described in Example 1:

                                      TABLE 1                                      __________________________________________________________________________      ##STR28##                                                                     __________________________________________________________________________                             Melting                                                                             Boiling                                           Example                 point                                                                               point  Recrystallised                             No.  X           R      [°C.]                                                                        [°C./mm Hg]                                                                    from                                       __________________________________________________________________________     2    CF.sub.3    CH.sub.3    51/0.09                                           3    CF.sub.3    C.sub.4 H.sub.9 (i)                                                                        66-69/0.07                                        4    CN          CH.sub.3                                                                              48-50       Ligroin                                    5    CN          C.sub.4 H.sub.9 (i)                                                                   47-49       Ligroin                                    6    CN                                                                                          ##STR29##                                                                            33-34       --                                         7    CN                                                                                          ##STR30##                                                                            70-71       wash benzine                               8    CN                                                                                          ##STR31##                                                                            100- 101    wash benzine                                     ##STR32##  CH.sub.3                                                                              33-35       --                                         10                                                                                   ##STR33##  C.sub.2 H.sub.5                                                                       30   130-132/0.1                                       11                                                                                   ##STR34##  C.sub.4 H.sub.9 (i)                                                                        112-115/0.08                                      12                                                                                   ##STR35##  C.sub.4 H.sub.9 (i)                                                                        133-136/0.09                                      13                                                                                   ##STR36##  C.sub.4 H.sub.9 (i)                                                                   122- 124    wash benzine                               14                                                                                   ##STR37##  C.sub.4 H.sub.9 (i)                                                                   65-66       wash benzine                               15                                                                                   ##STR38##  CH.sub.3                                                                              62-63       ligroin                                    16                                                                                   ##STR39##  C.sub.2 H.sub.5                                                                       76-78       wash benzine                               17                                                                                   ##STR40##  C.sub.4 H.sub.9 (i)                                                                   29-30       --                                         18                                                                                   ##STR41##  C.sub.4 H.sub.9 (i)                                                                   36-37       --                                         19                                                                                   ##STR42##  CH.sub.3                                                                              64          Ligroin                                    __________________________________________________________________________                                  Boiling                                                                        point                                                                     Melting                                                                             [°C./mm Hg]                                Example                 point                                                                               or refract-                                                                            Recrystallised                            No.  X           R      [°C.]                                                                        ive index                                                                              from                                      __________________________________________________________________________     20                                                                                   ##STR43##  C.sub.2 H.sub.5                                                                       73-75        Ligroin                                   21                                                                                   ##STR44##  C.sub.4 H.sub.9 (i)                                                                   65-66        Ligroin                                   22                                                                                   ##STR45##                                                                                  ##STR46##                                                                            94-95        Ligroin                                   23                                                                                   ##STR47##                                                                                  ##STR48##  n.sub.D.sup.20 : 1.5718                           24                                                                                   ##STR49##  C.sub.4 H.sub.9 (i)                                                                   37-38        --                                        25                                                                                   ##STR50##  CH.sub.3                                                                              --   n.sub.D.sup.20 : 1.5017                                                                --                                        26                                                                                   ##STR51##  C.sub.2 H.sub. 5                                                                      --   n.sub.D.sup.20 : 1.5129                                                                --                                        27                                                                                   ##STR52##  C.sub.3 H.sub.7                                                                       --   n.sub.D.sup.20 : 1.5017                                                                --                                        28                                                                                   ##STR53##  C.sub.3 H.sub.7 (i)                                                                   50-52        Ligroin                                   29                                                                                   ##STR54##  C.sub.4 H.sub.9                                                                       35           Ligroin                                   30                                                                                   ##STR55##  C.sub.4 H.sub.9 (i)                                                                   55           Ligroin                                   31                                                                                   ##STR56##                                                                                  ##STR57##                                                                            --   n.sub.D.sup.20 : 1.5436                                                                --                                        32                                                                                   ##STR58##  CH.sub.3                                                                              92-94        wash benzine                              33                                                                                   ##STR59##  C.sub.4 H.sub.9 (i)                                                                   --   n.sub.D.sup.20 : 1.5564                           34                                                                                   ##STR60##  C.sub.4 H.sub.9 (i)                                                                   --   n.sub.D.sup.20 : 1.5391                           35                                                                                   ##STR61##  CH.sub.3                                                                              141- 143     wash benzine                              36                                                                                   ##STR62##  C.sub.2 H.sub.5                                                                       120- 121     Ligroin                                   37                                                                                   ##STR63##  C.sub.4 H.sub.9 (i)                                                                   109- 111     wash benzine                              38                                                                                   ##STR64##  C.sub.4 H.sub.9 (i)                                                                        123-125/0.08                                                                           --                                        39                                                                                   ##STR65##  C.sub.4 H.sub.9 (i)                                                                        n.sub.D.sup.20 : 1.5182                           40                                                                                   ##STR66##                                                                                  ##STR67##  n.sub.D.sup.20 : 1.5220                           __________________________________________________________________________

PREPARATION OF THE STARTING MATERIALS EXAMPLE 41 ##STR68##

380 g (2 mol) of 4,5-dichloro-2-trichloromethylimidazole were initially introduced into a fluorination autoclave and 400 ml of hydrogen fluoride were added at 0° C. The autoclave was closed and a blanketing pressure of 2 atmospheres of chlorine was applied. The mixture was heated up to 100° C. in the course of 2 hours and then up to 140° C. in the course of a further 2 hours and this temperature was maintained for a further three and half hours. The pressure, which rose due to the hydrogen chloride formed, was let down by means of a condenser with the aid of a control valve set at 20 bars. After the reaction had ended, the mixture was allowed to cool, the pressure was let down and excess hydrogen fluoride was distilled off. The residue was dissolved in tetrahydrofuran; sodium fluoride was added to this solution and the mixture was shaken and filtered. After stirring off the solvent, 262 g (85.5% of theory) of 4,5-dichloro-2-trifluoromethyl-imidazole were obtained in the form of a crystalline product with a melting point of 186°-188° C.

EXAMPLE 42 ##STR69##

25.4 g (0.1 mol) of 4,5-dichloro-2-trichloromethylimidazole were introduced in small portions into 200 ml of ethanol saturated with ammonia, whilst cooling with ice and stirring vigorously. The mixture was stirred for a further 30 minutes at 50° C., the constituents which had not dissolved were then filtered off and the filtrate was evaporated under reduced pressure. The combined residues were dissolved in hot water. On acidifying the solution with dilute hydrochloric acid, the reaction product precipited out. This was filtered off, washed with water and dried. In this way 14.6 g (90% of theory) of 4,5-dichloro-2-cyano-imidazole were obtained and after recrystallisation from toluene this had a melting point of 187°-189° C.

EXAMPLE 43 ##STR70##

560 g (2.56 mol) of 4,5-dichloro-2-dichloromethyleneimidazole were added to 1 kg (13.2 mol) of glycol monomethyl ether, whilst cooling slightly and stirring, at such a rate that the temperature of the exothermic reaction was maintained at 80°-100° C. Thereafter the reaction mixture was evaporated to dryness in vacuo. This gave 4,5-dichloro-imidazole-2-carboxylic acid methoxyethyl ester in virtually quantitative yield. Melting point 130° C.

The same compound was obtained if 4,5-dichloro-2-trichloromethylimidazole was employed in place of 4,5-dichloro-2-dichloromethyleneimidazole. The reaction was carried out in the manner described above. However, it was appropriate to heat the reaction mixture to 90°-100° C. for a while after the addition of the 4,5-dichloro-2-trichloromethyl-imidazole was complete.

EXAMPLE 44 ##STR71##

Using the method described in Example 43, the reaction of isopropanol with 4,5-dichloro-2-dichloromethylene-imidazole gave 4,5-dichloro-imidazole-2-carboxylic acid isopropyl ester as a crystalline product of melting point 168° C.

EXAMPLE 45 ##STR72##

21.9 g (0.2 mol) of diethylamine hydrochloride are added to a solution of 21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethylene-imidazole in 100 ml of dioxan and the mixture was heated to the reflux temperature for 2 hours, whilst stirring. It was then allowed to cool and water was added. The product which hereupon precipitated was filtered off, washed with water and dried 18 g (7.6% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid diethylamide, having a melting point of 119° C. after recrystallisation from acetonitrile, were thus obtained.

EXAMPLE 46 ##STR73## Variant (a)

654 g (3 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in a finely powdered form were added, in portions, in the course of about one hour to a mixture, which had been initially introduced, of 783 g (9 mol) of isopropylformamide, 162 g (9 mol) of water and 3 liter of acetonitrile, at 0° C., whilst stirring and whilst cooling. The clear solution was then poured into 15 kg of ice water. The resulting white precipitate was filtered off, washed with water and dried. This gave 630 g (84% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid N-formyl-isopropylamide with a melting point of 142° C. The same result was also obtained without the addition of water.

Variant (b)

21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in a finely powdered form were added in portions to 87 g (1 mol) of isopropyl-formamide, whilst stirring, and the reaction mixture warmed up to 40°-50° C. After the exothermic reaction had subsided, the reaction mixture was poured into excess ice water. A viscous precipitate first formed and this solidified after standing for about one hour. After the product had been filtered off, washed with water and dried, 23 g of a substance were obtained, the major part of which was identical with the product described under (a). Melting range about 132°-137° C. By fractional crystallisation from acetonitrile, it was possible, after separating off a more sparingly soluble secondary component, to isolate the product described under (a) in a pure form with a melting point of 142° C.

EXAMPLE 47 ##STR74## Variant (a)

From 4,5-dichloro-imidazole-2-carboxylic acid N-formylisopropylamide (see Example 46):

25 g (0.1 mol) of 4,5-dichloro-imidazole-2-carboxylic acid N-formyl-isopropylamide were stirred with 200 ml of concentrated sulphuric acid for about 15 minutes at 50°-70° C. After cooling, the reaction mixture was poured onto ice. The solid thus obtained was filtered off, washed with water until neutral and dried. This gave 16 g (72% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid ispropylamide with a melting point of 150° C.

Variant (b)

From 4,5-dichloro-2-dichloromethylene-imidazole ("one-vessel process"):

654 g (3 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in a finely powdered form were added in portions in the course of about one hour to a mixture, which had been initially introduced, of 783 g (9 mol) of isopropylformamide and 162 g (9 mol) of water, whilst stirring and with gentle cooling, and the internal temperature rose to about 75° C. Subsequently, the mixture was heated to about 90°-110° C. for a further half hour. After cooling, the product was precipitated in water, filtered off, washed with water and dried. This gave 566 g (85% of theory) of 4,5-dichloroimidazole-2-carboxylic acid isopropylamide with a melting point of 150° C.

The compounds listed in Table 2 below were obtained in accordance with methods analogous to those described in Example 47:

                  TABLE 2                                                          ______________________________________                                          ##STR75##                                                                     Example                      Melting                                           No.      R.sup.3             point (°C.)                                ______________________________________                                         48       H                   260                                               49       CH.sub.3            240                                               50       C.sub.2 H.sub.5     146                                               51       CH.sub.2CH.sub.2CH.sub.3                                                                           140                                               52       CH.sub.2CH.sub.2CH.sub.2CH.sub.3                                                                   105                                               53       tert.-C.sub.4 H.sub.9                                                                              218                                               54                                                                                       ##STR76##          186                                               55                                                                                       ##STR77##          172                                               ______________________________________                                    

EXAMPLE 56 ##STR78##

21.8 g (0.1 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in the form of a fine powder were added to a mixture of 16 g (0.125 mol) of 2-chloroaniline in the form of a fine powder, 100 ml of water and 15 g (about 0.15 mol) of 37% strength aqueous hydrochloric acid at room temperature, whilst stirring, and the mixture was then heated to about 100° C. for about 1 hour. After it had cooled, zhe product which had precipitated was filtered off, washed with water and dried. 21.5 g (74% of theory) of 4,5-dichloro-imidazole-2-carboxylic acid 2-chloroanilide of melting point 244° C. were thus obtained.

EXAMPLE 57 ##STR79##

Using the method described in Example 56, the reaction of 3-trifluoromethylaniline with 4,5-dichloro-2-dichloromethylene-imidazole gave 4,5-dichloro-imidazole-2-carboxylic acid 3-trifuloromethylanilide as a crystalline product which had a melting point of 200° C. after recrystallisation from toluene.

EXAMPLE 58 ##STR80##

Dry hydrogen chloride was passed into a solution of 218 g (1.0 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in about 2 liters of dry toluene until the formation of a precipitate had ended (at least 1 mol). After cooling (the HCl addition took place exothermically), filtering off and drying, 235 g (89% of theory) of 4,5-dichloro-2-trichloromethyl-imidazole of melting point 210° C. (with decomposition) were obtained.

EXAMPLE 59 ##STR81##

40 g (0.55 mol) of dimethylformamide were added dropwise in the course of about 10 minutes to a boiling solution of 100 g (0.46 mol) of 4,5-dichloro-2-dichloromethyleneimidazole in 1 liter of petroleum ether (boiling range about 60° C.) and a precipitate separated out. After cooling, the petroleum ether was decanted off and the precipitate was stirred with acetone. Subsequently it was filtered off and washed with acetone until the acetone which ran off was pale yellow. This gave 41 g (55% theory) of the dimeric ketene of the above formula in the form of a pale yellow powder with a melting point of above 290° C. 

What is claimed is:
 1. A 4,5-dichloro-imidazole of the formula ##STR82## in which X represents a ##STR83## in which R² represents hydrogen or an alkyl with 1 to 8 carbon atoms,R³ represents cyclopentyl or cyclohexyl or represents phenyl which can carry a trifluoromethyl group, and R represents alkyl with 1 to 12 carbon atoms, it being possible for each of these alkyl radicals to carry phenyl (which itself can carry one or more substituents selected from alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, halogen and trifluoromethyl), or represents cycloalkyl with 5 or 6 carbon atoms in the ring or represents a phenyl radical which is at least disubstituted.
 2. A 4,5-dichloro-imidazole according to claim 1 whereinR² represents hydrogen, straight-chain or branched alkyl with 1 to 6 carbon atoms, R represents straight-chain or branched alkyl with 1 to 6 carbon atoms, it being possible for each of these radicals to carry a phenyl substituent, or represents cycloalkyl with 5 or 6 carbon atoms in the ring or phenyl which has identical or different substituents at least in the 2- and 4-positions, the substituents being selected from the group consisting of methyl and halogen. 